Metal-organic framework nanocrystal loaded polyurethane foam as well as preparation and application thereof

Abstract

The invention discloses a metal-organic framework nanocrystal loaded polyurethane foam as well as a preparation and an application thereof. Polyurethane prepolymer and active amino on MOFs (Metal-Organic Frameworks) are taken to perform chemical doping, the great challenge that MOFs materials are difficult to process is overcome, MOFs nanoparticles are uniformly loaded in the polyurethane foam, a foam reactor is obtained by means of in-situ forming, a new process of building a complex mesoporous-microporous assembly based on microporous metal-organic skeleton nanoparticles as structural units is provided to observe catalysis of the MOFs nanoparticles on knoevenagel condensation; as water serves as a foaming agent and a green chemical method is adopted to prepare an integral flow-by foam reactor to catalyze an organic reaction, aftertreatment of a catalyst is simplified, loss of the catalyst is avoided, continuous flow-by cyclic catalyzation can also be performed, and a new method is provided for the treatment of environmental pollution and chemical industry.

Description

technical field

[0001] The invention relates to a polyurethane foam reactor loaded with metal-organic framework nanocrystals and its preparation method and application, belonging to the technical field of polymer functional materials. Background technique

[0002] Metal-organic frameworks (MOFs) are a new type of porous inorganic-organic hybrid crystalline material, which is composed of metal ions or metal clusters connected with organic ligands through covalent bonds. It exhibits the characteristics of both organic and inorganic materials. High porosity, controllable channels, structural diversity, rich functionality, simple preparation, etc. These unique advantages have attracted widespread attention. MOFs membrane materials have the characteristics of high efficiency, energy saving, economy, etc., and the application range can be extended to liquid and some gaseous media, such as membrane separation, fluorescence sensing, etc., so it has attracted extensive attention. Ho...

Examples

Embodiment 1

[0054] Example 1 Metal Organic Framework UiO-66-NH 2 Synthesis

[0055] Dissolve the organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, and acetic acid in N,N-dimethylformamide solvent, keep the temperature at 120°C for 24 hours, and cool down to room temperature to obtain light yellow nano-sized crystals, centrifuge, Drying; wherein the ratio of organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, acetic acid and N,N-dimethylformamide solvent addition is 0.04mmol: 0.04mmol: 2mmol: 1.6ml, the obtained crystal See in description figure 1 .

Embodiment 2

[0056] Example 2 metal organic framework MIL-101-NH 2 -Synthesis of (Fe)

[0057] The organic ligand 2-aminoterephthalic acid (1.09g, 6mmol) and ferric chloride hexahydrate (1.08g, 4mmol) were dissolved in 20mL DMF, placed in a crystallization axe, and kept at 110°C for 16h. Cool down to room temperature to obtain gray nanoscale crystals, centrifuge, wash with DMF and ethanol in turn, and dry at 120 degrees Celsius for 24 hours to obtain MIL-101-NH 2 -(Fe) crystalline powder, XRD results see figure 2 .

Embodiment 3

[0058] The synthesis of embodiment 3 polyether diol type polyurethane prepolymer

[0059] Add 37g of 4,4-diphenylmethane diisocyanate (MDI) and 63g of PPO (polypropylene oxide) with a molecular weight of 2000 into the reaction vessel in sequence, stir at 80°C, and react at constant temperature for 4 hours, then stop Heating, removing unreacted small molecules by vacuum distillation to obtain a prepolymer with NCO=10-11, viscosity 2000-3000mPa.s, GPC curve see image 3 , see the NMR spectrum Figure 4 .

technical field

[0001] The invention relates to a polyurethane foam reactor loaded with metal-organic framework nanocrystals and its preparation method and application, belonging to the technical field of polymer functional materials. Background technique

[0002] Metal-organic frameworks (MOFs) are a new type of porous inorganic-organic hybrid crystalline material, which is composed of metal ions or metal clusters connected with organic ligands through covalent bonds. It exhibits the characteristics of both organic and inorganic materials. High porosity, controllable channels, structural diversity, rich functionality, simple preparation, etc. These unique advantages have attracted widespread attention. MOFs membrane materials have the characteristics of high efficiency, energy saving, economy, etc., and the application range can be extended to liquid and some gaseous media, such as membrane separation, fluorescence sensing, etc., so it has attracted extensive attention. Ho...

Examples

Embodiment 1

[0054] Example 1 Metal Organic Framework UiO-66-NH 2 Synthesis

[0055] Dissolve the organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, and acetic acid in N,N-dimethylformamide solvent, keep the temperature at 120°C for 24 hours, and cool down to room temperature to obtain light yellow nano-sized crystals, centrifuge, Drying; wherein the ratio of organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, acetic acid and N,N-dimethylformamide solvent addition is 0.04mmol: 0.04mmol: 2mmol: 1.6ml, the obtained crystal See in description figure 1 .

Embodiment 2

[0056] Example 2 metal organic framework MIL-101-NH 2 -Synthesis of (Fe)

[0057] The organic ligand 2-aminoterephthalic acid (1.09g, 6mmol) and ferric chloride hexahydrate (1.08g, 4mmol) were dissolved in 20mL DMF, placed in a crystallization axe, and kept at 110°C for 16h. Cool down to room temperature to obtain gray nanoscale crystals, centrifuge, wash with DMF and ethanol in turn, and dry at 120 degrees Celsius for 24 hours to obtain MIL-101-NH 2 -(Fe) crystalline powder, XRD results see figure 2 .

Embodiment 3

[0058] The synthesis of embodiment 3 polyether diol type polyurethane prepolymer

[0059] Add 37g of 4,4-diphenylmethane diisocyanate (MDI) and 63g of PPO (polypropylene oxide) with a molecular weight of 2000 into the reaction vessel in sequence, stir at 80°C, and react at constant temperature for 4 hours, then stop Heating, removing unreacted small molecules by vacuum distillation to obtain a prepolymer with NCO=10-11, viscosity 2000-3000mPa.s, GPC curve see image 3 , see the NMR spectrum Figure 4 .

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